CN102558420A - Vinyl acetate copolymer modified by silsesquioxane (tris sulfonic acid isobutyl polyhedral oligomeric silsesquioxane (POSS)) and preparation method thereof - Google Patents
Vinyl acetate copolymer modified by silsesquioxane (tris sulfonic acid isobutyl polyhedral oligomeric silsesquioxane (POSS)) and preparation method thereof Download PDFInfo
- Publication number
- CN102558420A CN102558420A CN2011104484043A CN201110448404A CN102558420A CN 102558420 A CN102558420 A CN 102558420A CN 2011104484043 A CN2011104484043 A CN 2011104484043A CN 201110448404 A CN201110448404 A CN 201110448404A CN 102558420 A CN102558420 A CN 102558420A
- Authority
- CN
- China
- Prior art keywords
- vinyl acetate
- acetate copolymer
- silsesquioxane
- poss
- modification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
A vinyl acetate copolymer modified by silsesquioxane (tris sulfonic acid isobutyl polyhedral oligomeric silsesquioxane (POSS)) and a preparation method of the copolymer are disclosed, and a vinyl acetate copolymer is related. The invention provides the vinyl acetate copolymer modified by POSS and the preparation method of the copolymer. The vinyl acetate copolymer modified by POSS has the components in mass parts of: 35-45 parts of vinyl acetate; 10-15 parts of modified monomer, 0.5-1 parts of initiator; 2.5-5 parts of compound emulsifier; 4-6 parts of colloid protecting agent; and 40-60 parts of deionized water. Using an amphiphilic organic/inorganic hybrid enhanced material with surface activity as an emulsifier in the polymer synthesis process, enables the rigid cage structure of POSS to be effectively combined on the surface of the polymer. The modified vinyl acetate copolymer has an outer layer of the POSS nano reinforced material; and an inner layer of the vinyl acetate copolymer with a core-shell structure, thereby improving the usabilities of the polymer material such as water resistance, surface hardness and the like.
Description
Technical field
The present invention relates to a kind of vinyl acetate copolymer, particularly relate to vinyl acetate copolymer of a kind of silsesquioxane modification and preparation method thereof.
Background technology
That the Vinyl Acetate Copolymer (PVAc) for preparing through emulsion polymerisation process has is cheap, easy to use, glue performance is good, series of advantages such as nontoxic, free from environmental pollution, has been widely used in the gummed of porous materials such as timber, leather, paper, porous plastics.But acetate emulsion also exists water tolerance, frost resistance, creep resistant relatively poor, the not high shortcoming of thermotolerance.Along with science and technology and expanding economy; Some Application Areass have proposed the more property requirement to polyvinyl acetate; As: winter hardiness, stability, water tolerance, thermotolerance, high solids content, high-adhesive-strength etc., all polyvinyl acetate emulsion can not satisfy above-mentioned requirements simultaneously.Therefore, the Dichlorodiphenyl Acetate Alathon carries out modification, widens Application Areas, just becomes important research project.
Chen Ping Yao (Chinese patent; CN102040928A; A kind of modification water-resistant anti-freezing latex) use vinyl acetate between to for plastic and modified monomer copolymerization, the method that adds modified additives such as antifreezing agent, mould inhibitor, softening agent prepares the vinyl acetate copolymer that possesses certain water-resistant anti-freezing performance.Wang Haitao (Chinese patent, CN101121768A, polyvinyl acetate copolymerization emulsion) provides a kind of method of utilizing emulsion polymerisation process to prepare polyvinyl acetate copolymer, with the problem of the dispersiveness that solves common aqueous polyvinyl acetate emulsion.Bang English (methylacrylic acid adhesive of modified polyvinyl acetate emulsion research [J]. bonding; 2009; 33～36) adopt the semi-continuous seed emulsion polymerization method to prepare vinyl acetate between to for plastic/tertiary ethylene carbonate/methylacrylic acid ternary copolymer emulsion, the conductometry analysis is after vinyl acetate between to for plastic and the methylacrylic acid copolymerization; The part carboxylic group is scattered in the latex particle surface, has improved the water resistance of emulsion.Shi Weiyun (a kind of research of modification acetate emulsion copolymerization coating and application [J]. contemporary chemical industry; 2006; 35 (3); 177～178) utilize vinyl acetate, Bing Xisuandingzhi, TEB 3K, vinylformic acid as filmogen, copolymerization obtains a kind of modification acetate emulsion, to improve coating film-forming properties and water tolerance.Zhang Xiaowei (development [J] of vinylformic acid (ester) modified polyvinyl acetate emulsion. Chinese tackiness agent; 2008; 17 (3), 32～36) adopt the semi-continuous seed emulsion polymerization method, use acrylate functional property monomer, Bing Xisuandingzhi soft monomer Dichlorodiphenyl Acetate vinyl acetate to carry out modification by copolymerization; Prepare the PVA modified emulsion of high solids content, its water tolerance and resistance to acids and bases be improved significantly.
Summary of the invention
The object of the invention aims to provide vinyl acetate copolymer of a kind of silsesquioxane modification and preparation method thereof.Polyvinyl acetate copolymer skin through modification contains the silsesquioxane nano strongthener, and internal layer is the vinyl acetate copolymer of nucleocapsid structure, can promote use propertieies such as water tolerance, surface hardness significantly.
The vinyl acetate copolymer of said silsesquioxane modification consists of vinyl acetate 35～45 by mass ratio; Modified monomer 10～15; Initiator 0.5～1; Compound emulsifying agent 2.5～5; Colloid protective agent 4～6; Deionized water 40～60.
Said modified monomer is mixed by TEB 3K, Jia Jibingxisuanyizhi, NSC 20956, vinylformic acid, Rocryl 400 and forms, and consists of TEB 3K 1～2, Jia Jibingxisuanyizhi 2～3, NSC 20956 2～3, vinylformic acid 2～3, Rocryl 400 3～4 by mass ratio.
Said initiator can be selected from ammonium persulphate etc.
Said compound emulsifying agent is made up of silsesquioxane and octyl phenol polyoxy ethene (10) ether (OP-10), presses mass ratio, silsesquioxane: octyl phenol polyoxy ethene (10) ether (OP-10) is 1: 1; Said silsesquioxane is trisulfonic acid fundamental mode isobutyl-silsesquioxane (Tris Sulfonic Acid Isobutyl POSS); This is that a kind of hybrid nano material (abbreviates as: POSS); Size 1.5～the 3.0nm of its cage shape silica structure, structural formula is following:
Said colloid protective agent is optional from Z 150PH etc.
The preparation method of the vinyl acetate copolymer of said silsesquioxane modification may further comprise the steps:
1) in the four-hole boiling flask reaction unit of being furnished with whisking appliance, reflux condensing tube, 2 tap funnels, puts into magnet rotor; Add ionized water and Z 150PH by proportioning raw materials; Heating in water bath is opened condensing reflux, stirring, regulates water temperature to 45～50 and ℃ dissolves fully until Z 150PH;
2) regulate water temperature to 65～75 ℃, add compound emulsifying agent, initiator by proportioning raw materials, add then after vinyl acetate and modified monomer react, slaking adds NaHCO between the rapid steam ager
3Regulating the pH value is 6～7, gets the vinyl acetate copolymer of silsesquioxane modification.
In step 2) in, the time of said reaction can be 1～1.5h, and the condition of said slaking can be at 75 ℃ of following slaking 20～40min; Said NaHCO
3Concentration can be 0.1mol/L.
Polyvinyl acetate copolymer based on surfactivity silsesquioxane nano material enhancing modified according to the invention has following remarkable advantage: (1) the present invention will have surface-active amphiphilic hybrid strongthener and be applied to the polymkeric substance building-up process as emulsifying agent; Make POSS rigidity cage structure effectively be combined in polymer surfaces, thereby improve polymer materials water tolerance, wear resistance.Its concrete mechanism of action is following: at first POSS is present in the emulsion particle surface as tensio-active agent; Form outer POSS structure A; The nucleocapsid structure B (as shown in Figure 1) of internal layer vinyl acetate copolymer; Tris Sulfonic Acid Isobutyl POSS is different from SiO2, organosilicon and other fillers, and it is a kind of inorganic-organic blended mixture with nano-scale and cage structure, and the cage structure that its Si-O key constitutes has very strong rigidity; The isobutyl-of its peripheral parcel makes itself and polymkeric substance and organic monomer that good consistency arranged on nanostructure size; And the backbone that contains hydroxyl and ehter bond possesses wetting ability, and this amphiphilic structure makes it possess influence of surfactant, is prone to be wrapped in the copolymer artcle surface with the polymer formation nucleocapsid structure; As shown in Figure 2, the small-particle on surface is the POSS of moving to the surface in the three-dimensional arrangement.After multipolymer is coated on wood product surface, the breakdown of emulsion along with the evaporation of moisture, the inner multipolymer of emulsion particle contacts with each other; And then film forming, the POSS structure is further to surface transport (as shown in Figure 3, the small-particle on surface is the POSS of moving to the surface) simultaneously; Behind the last moisture evaporate to dryness, POSS surface hydrophilic group is imbedded polymkeric substance inside because of the polarity effect, and the rigidity cage structure of POSS effectively is combined in the surface of polymeric coating; The high top coat water-fast, wear resisting property of final formation is (as shown in Figure 4; A is POSS among the figure, and B is a vinyl acetate copolymer, and C is the woodwork material).(2) selecting different methacrylic esters is modification soft or hard monomer; Comprise TEB 3K, Jia Jibingxisuanyizhi, NSC 20956 etc.; In order to the second-order transition temperature of control copolymerization system, regulate the film-forming temperature and the water tolerance of vinyl acetate between to for plastic ester articles.(3) select monomer that vinylformic acid, Rocryl 400 etc. have hydroxyl and carboxyl as the modification function monomer, make raw material in polymerization process, can form partly in crosslinked, water tolerance, stability and the viscosity of raising goods.
Description of drawings
Fig. 1 is the nucleocapsid structure synoptic diagram of the vinyl acetate copolymer of silsesquioxane modification.In Fig. 1, mark A is outer POSS structure, and B is the nucleocapsid structure of internal layer vinyl acetate copolymer.
Fig. 2 is a copolymer molecule view before the breakdown of emulsion.In Fig. 2, upward be cross-section structure, be three-dimensional arrangement down.
Fig. 3 for multipolymer because of the film forming process synoptic diagram of moisture evaporation breakdown of emulsion.
Fig. 4 is covered in the coating synoptic diagram that wood product surface forms for multipolymer.In Fig. 4, mark A is POSS, and B is a vinyl acetate copolymer, and C is the woodwork material.
Embodiment
Through embodiment the present invention is described further below.
Embodiment 1
On the 500ml four-hole boiling flask, build the reaction unit that contains whisking appliance, reflux condensing tube, tap funnel (2), in four-hole boiling flask, put into magnet rotor, the back adds removes 50ml ionized water, 6g Z 150PH.Device is put into digital display intelligent temperature control magnetic stirring apparatus heating in water bath, opens condensing reflux, stirring, regulates rotating speed, regulates water temperature to 50 and ℃ dissolves fully until Z 150PH.2g TEB 3K, 3g Jia Jibingxisuanyizhi, 3g NSC 20956,3g vinylformic acid, 4g Rocryl 400 are mixed the back and add in the tap funnel.Regulate water temperature to 65 ℃; In four-hole boiling flask, add 3ml 4%OP-10 solution, 3g Tris Sulfonic Acid Isobutyl POSS (Hybrid Plastics Company products); 1g ammonium persulphate (using the 10ml deionized water dissolving); Begin to drip vinyl acetate between to for plastic and the 15g modified monomer mixed solution of 45g simultaneously, reacted 1.5 hours.After reaction is accomplished, continue to maintain the temperature at 75 ℃ of slaking half a hour, discharging then drips 0.1mol/LNaHCO between the rapid steam ager
3Regulating the pH value is 6.5.
Product performance index detects as follows:
Proterties: oyster white, no coarse particles and foreign matter; Using laboratory pH meter PHSJ-4A to detect pH is 6.5; It is 61% that oven method detects solid content; Use NDJ-1 type rotational viscosimeter to detect viscosity and be 10.1Pas; Detect with reference to compressed detected TP among the HG/T2727-95 (aqueous polyvinyl acetate emulsion timber sizing agent), dry strength is 9.1MPa, and wet tenacity is 5.3MPA; The timber contaminative: the colour developing that applies ferrous sulfate is shallow; According to standard GB/T1733-93, the paint film water tolerance is detected, no loss of gloss, variable color, foaming, wrinkling, phenomenon such as come off, water-intake rate is 11%; According to GB/T6739-1966, utilize hardness of film pencil assay method to detect hardness of film and be 5H.
Embodiment 2
On the 500ml four-hole boiling flask, build the reaction unit that contains whisking appliance, reflux condensing tube, tap funnel (2), in four-hole boiling flask, put into magnet rotor, the back adds removes 30ml ionized water, 4g Z 150PH.Device is put into digital display intelligent temperature control magnetic stirring apparatus heating in water bath, opens condensing reflux, stirring, suitably regulates rotating speed, regulates water temperature to 50 and ℃ dissolves fully until Z 150PH.1g TEB 3K, 2g Jia Jibingxisuanyizhi, 2g NSC 20956,2g vinylformic acid, 3g Rocryl 400 are mixed the back adding to drip in the funnel at night.Regulate water temperature to 70 ℃; In four-hole boiling flask, add 2ml 4%OP-10 solution, 2g Tris Sulfonic Acid Isobutyl POSS; 0.4g ammonium persulphate (using the 10ml deionized water dissolving), vinyl acetate between to for plastic and the 10g modified monomer mixed solution of Dropwise 35 g reacted 1 hour simultaneously., after reaction is accomplished, continuing to maintain the temperature at 75 ℃ of slaking half a hour, discharging then drips 0.1mol/LNaHCO between the rapid steam ager
3Regulating the pH value is 7.
Product performance index detects as follows:
Proterties: oyster white, no coarse particles and foreign matter; Using laboratory pH meter PHSJ-4A to detect pH is 7; It is 58% that oven method detects solid content; Use NDJ-1 type rotational viscosimeter to detect viscosity and be 8.9Pas; Detect with reference to compressed detected TP among the HG/T2727-95 (aqueous polyvinyl acetate emulsion timber sizing agent), dry strength is 7MPa, and wet tenacity is 4.5MPA, the timber contaminative: the colour developing that applies ferrous sulfate is shallow.According to standard GB/T1733-93, the paint film water tolerance is detected, no loss of gloss, variable color, foaming, wrinkling, phenomenon such as come off, water-intake rate is 10.3%; According to GB/T6739-1966, utilize hardness of film pencil assay method to detect hardness of film and be 5H.
Embodiment 3
On the 500ml four-hole boiling flask, build the reaction unit that contains whisking appliance, reflux condensing tube, tap funnel (2), in four-hole boiling flask, put into magnet rotor, the back adds removes 40ml ionized water, 4.5g Z 150PH.Device is put into digital display intelligent temperature control magnetic stirring apparatus heating in water bath, opens condensing reflux, stirring, suitably regulates rotating speed, regulates water temperature to 50 ℃ to Z 150PH and dissolves fully.1.5g TEB 3K, 2.5g Jia Jibingxisuanyizhi, 2.5g NSC 20956,2.5g vinylformic acid, 3.5g Rocryl 400 are mixed the back adding to drip in the funnel at night.Regulate water temperature to 70 ℃; In four-hole boiling flask, add 2.5ml4%OP-10 solution, 2.5g Tris Sulfonic Acid Isobutyl POSS; 0.6g ammonium persulphate (using the 10ml deionized water dissolving) drips vinyl acetate between to for plastic and the 13.5g modified monomer mixed solution of 40g simultaneously, reacts 1 hour.After reaction is accomplished, continue to maintain the temperature at 75 ℃ of slaking half a hour, discharging then drips 0.1mol/LNaHCO between the rapid steam ager
3Regulating the pH value is 6.
Product performance index detects as follows:
Proterties: oyster white, no coarse particles and foreign matter; Using laboratory pH meter PHSJ-4A to detect pH is 6; It is 65% that oven method detects solid content; Use NDJ-1 type rotational viscosimeter to detect viscosity and be 10.5Pas; Detect with reference to compressed detected TP among the HG/T2727-95 (aqueous polyvinyl acetate emulsion timber sizing agent), dry strength is 10.1MPa, and wet tenacity is 7.9MPA, the timber contaminative: the colour developing that applies ferrous sulfate is shallow.According to standard GB/T1733-93, the paint film water tolerance is detected, no loss of gloss, variable color, foaming, wrinkling, phenomenon such as come off, water-intake rate is 11.1%; According to GB/T6739-1966, utilize hardness of film pencil assay method to detect hardness of film and be 5H.
Claims (8)
1. the vinyl acetate copolymer of a silsesquioxane modification is characterized in that consisting of vinyl acetate 35～45 by mass ratio; Modified monomer 10～15; Initiator 0.5～1; Compound emulsifying agent 2.5～5; Colloid protective agent 4～6; Deionized water 40～60.
2. the vinyl acetate copolymer of a kind of silsesquioxane modification as claimed in claim 1; It is characterized in that said modified monomer is mixed by TEB 3K, Jia Jibingxisuanyizhi, NSC 20956, vinylformic acid, Rocryl 400 forms, and consists of TEB 3K 1～2, Jia Jibingxisuanyizhi 2～3, NSC 20956 2～3, vinylformic acid 2～3, Rocryl 400 3～4 by mass ratio.
3. the vinyl acetate copolymer of a kind of silsesquioxane modification as claimed in claim 1 is characterized in that said initiator is an ammonium persulphate.
4. the vinyl acetate copolymer of a kind of silsesquioxane modification as claimed in claim 1; It is characterized in that said compound emulsifying agent is made up of silsesquioxane and octyl phenol polyoxy ethene (10) ether (OP-10); Press mass ratio, silsesquioxane: octyl phenol polyoxy ethene (10) ether (OP-10) is 1: 1; Said silsesquioxane is a trisulfonic acid fundamental mode isobutyl-silsesquioxane, the size 1.5～3.0nm of its cage shape silica structure, and structural formula is following:
5. the vinyl acetate copolymer of a kind of silsesquioxane modification as claimed in claim 1 is characterized in that said colloid protective agent is a Z 150PH.
6. the preparation method of the vinyl acetate copolymer of a kind of silsesquioxane modification as claimed in claim 1 is characterized in that may further comprise the steps:
1) in the four-hole boiling flask reaction unit of being furnished with whisking appliance, reflux condensing tube, 2 tap funnels, puts into magnet rotor; Add ionized water and Z 150PH by proportioning raw materials; Heating in water bath is opened condensing reflux, stirring, regulates water temperature to 45～50 and ℃ dissolves fully until Z 150PH;
2) regulate water temperature to 65～75 ℃, add compound emulsifying agent, initiator by proportioning raw materials, add then after vinyl acetate and modified monomer react, slaking adds NaHCO between the rapid steam ager
3Regulating the pH value is 6～7, gets the vinyl acetate copolymer of silsesquioxane modification.
7. the preparation method of the vinyl acetate copolymer of a kind of silsesquioxane modification as claimed in claim 6 is characterized in that in step 2) in, the time of said reaction is 1～1.5h, the condition of said slaking is at 75 ℃ of following slaking 20～40min.
8. the preparation method of the vinyl acetate copolymer of a kind of silsesquioxane modification as claimed in claim 6 is characterized in that in step 2) in, said NaHCO
3Concentration be 0.1mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110448404.3A CN102558420B (en) | 2011-12-28 | 2011-12-28 | Vinyl acetate copolymer modified by silsesquioxane (tris sulfonic acid isobutyl polyhedral oligomeric silsesquioxane (POSS)) and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110448404.3A CN102558420B (en) | 2011-12-28 | 2011-12-28 | Vinyl acetate copolymer modified by silsesquioxane (tris sulfonic acid isobutyl polyhedral oligomeric silsesquioxane (POSS)) and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102558420A true CN102558420A (en) | 2012-07-11 |
| CN102558420B CN102558420B (en) | 2014-05-28 |
Family
ID=46405143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110448404.3A Expired - Fee Related CN102558420B (en) | 2011-12-28 | 2011-12-28 | Vinyl acetate copolymer modified by silsesquioxane (tris sulfonic acid isobutyl polyhedral oligomeric silsesquioxane (POSS)) and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102558420B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106120442A (en) * | 2016-06-30 | 2016-11-16 | 上海锐瀚新材料科技有限公司 | A kind of antiseized emulsion of waterborne organic silicon and preparation method thereof |
| CN106947030A (en) * | 2017-03-27 | 2017-07-14 | 广东千色花化工有限公司 | POSS base hydridization polyacrylate dispersions and preparation method and application |
| CN112961548A (en) * | 2021-01-22 | 2021-06-15 | 湖北大学 | Organosilicon modified vinyl acetate ternary composition and preparation method thereof |
| CN114539688A (en) * | 2022-03-02 | 2022-05-27 | 常州市五洲环保科技有限公司 | Preparation method of plastic modified material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887921A (en) * | 2006-06-08 | 2007-01-03 | 武汉大学 | High performance organo-silicon modified vinyl acetate emulsion and its prepn |
| CN101121768A (en) * | 2007-09-19 | 2008-02-13 | 山西三维集团股份有限公司 | Polyvinyl acetate copolymerization emulsion |
| CN102040928A (en) * | 2010-11-24 | 2011-05-04 | 广东三和化工科技有限公司 | Modified waterproof frost-resisting white latex |
-
2011
- 2011-12-28 CN CN201110448404.3A patent/CN102558420B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887921A (en) * | 2006-06-08 | 2007-01-03 | 武汉大学 | High performance organo-silicon modified vinyl acetate emulsion and its prepn |
| CN101121768A (en) * | 2007-09-19 | 2008-02-13 | 山西三维集团股份有限公司 | Polyvinyl acetate copolymerization emulsion |
| CN102040928A (en) * | 2010-11-24 | 2011-05-04 | 广东三和化工科技有限公司 | Modified waterproof frost-resisting white latex |
Non-Patent Citations (1)
| Title |
|---|
| 孙心亚等: "有机硅氧烷改性醋酸乙烯酯-丙烯酸酯乳液的合成与性能", 《精细化工》, vol. 22, no. 8, 31 August 2005 (2005-08-31), pages 635 - 637 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106120442A (en) * | 2016-06-30 | 2016-11-16 | 上海锐瀚新材料科技有限公司 | A kind of antiseized emulsion of waterborne organic silicon and preparation method thereof |
| CN106120442B (en) * | 2016-06-30 | 2017-10-24 | 上海锐瀚新材料科技有限公司 | A kind of anti-sticking emulsion of waterborne organic silicon and preparation method thereof |
| CN106947030A (en) * | 2017-03-27 | 2017-07-14 | 广东千色花化工有限公司 | POSS base hydridization polyacrylate dispersions and preparation method and application |
| CN106947030B (en) * | 2017-03-27 | 2019-06-11 | 广东千色花化工有限公司 | POSS base hydridization polyacrylate dispersion and the preparation method and application thereof |
| CN112961548A (en) * | 2021-01-22 | 2021-06-15 | 湖北大学 | Organosilicon modified vinyl acetate ternary composition and preparation method thereof |
| CN112961548B (en) * | 2021-01-22 | 2021-12-03 | 湖北大学 | Organosilicon modified vinyl acetate ternary composition and preparation method thereof |
| CN114539688A (en) * | 2022-03-02 | 2022-05-27 | 常州市五洲环保科技有限公司 | Preparation method of plastic modified material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102558420B (en) | 2014-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101168577B (en) | Powdery compositions of dispersion polymers comprising gemini surfactants | |
| CN104109439B (en) | True mineral varnish of a kind of insulation and preparation method thereof | |
| CN102199239B (en) | Preparation method for acrylic acid microemulsion with self-crosslinking core-shell structure | |
| CN102027027B (en) | Nanoparticulate silicone organo copolymers and use thereof in coating means | |
| CN102702437B (en) | Styrene-acrylic emulsion as well as preparation method and application thereof | |
| CN102558420B (en) | Vinyl acetate copolymer modified by silsesquioxane (tris sulfonic acid isobutyl polyhedral oligomeric silsesquioxane (POSS)) and preparation method thereof | |
| CN106866869A (en) | A kind of preparation method of core shell structure hydroxyl acrylic emulsion | |
| CN102337704B (en) | Temperature-resisting printing paper water base varnish and preparation method thereof | |
| CN101220249A (en) | Green environment protection adhesion agent and production method | |
| CN108641050A (en) | A kind of preparation method of aqueous super hydrophobic material | |
| CN104011087B (en) | Aqueous polymer dispersions are used to improve the purposes to chemical affect tolerance | |
| CN102040928A (en) | Modified waterproof frost-resisting white latex | |
| CN105086892B (en) | A kind of enhanced water resistance aldehyde-free environment-friendly wood adhesive and preparation method thereof | |
| CN104558320B (en) | Polyvinyl acetate emulsion | |
| CN105237667A (en) | Preparation method of styrene-butadiene latex for carpets | |
| CN102559023B (en) | Scratch resistance waterborne polyurethane coating and preparation method thereof | |
| CN103215825B (en) | Printing adhesive of stone paper wallpaper and preparation method of printing adhesive | |
| CN102140217A (en) | Preparation method and use of polyacrylate/silica solution composite material | |
| CN102115512A (en) | Aqueous emulsion and aqueous paint | |
| PT1732997E (en) | Coating masses made from low-emission binding agents | |
| CN109627881A (en) | A kind of interface coating and preparation method thereof for waterproof | |
| CN105623417A (en) | Water-based low-temperature-curing fluorine-containing sealing element coating | |
| CN107406552A (en) | Polymer latex composition for fiber bonding | |
| CN104774506A (en) | Inorganic dry-powder transparent priming paint, and preparation method and applications thereof | |
| CN103819991B (en) | Protection material suitable for dinosaur fossil and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140528 Termination date: 20201228 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |